Core Emission Research Articles

LnIII-centered emission sensitized through fluorescent carbon dots

We synthesized CDs that were crystalline and monodisperse with average diameters in the range 4–5nm. The CDs had a fluorescence quantum yield of 0.20%, with emission lifetimes of 3.1 and 6.5ns attributed to surface and core emissions, respectively. 13C NMR spectroscopy indicated the presence of C–C, C˭C and C˭O groups on the surface of the CDs. Powder XRD and TEM indicate the CDs are graphitic. The CDs were decorated with LnIII ions through coordination to the surface carbonyl and carboxylato groups. When excited, the CDs transferred energy to the emissive states of the LnIII ions, which led to observation of the characteristic emission spectra of EuIII and TbIII with emission lifetimes of 1.00 and 0.63ms, respectively and with emission quantum yields of 0.17% and 1.43%, respectively.

A framed, 16-image Kirkpatrick-Baez x-ray microscope.

A 16-image Kirkpatrick-Baez (KB)-type x-ray microscope consisting of compact KB mirrors [F. J. Marshall, Rev. Sci. Instrum. 83, 10E518 (2012)] has been assembled for the first time with mirrors aligned to allow it to be coupled to a high-speed framing camera. The high-speed framing camera has four independently gated strips whose emission sampling interval is ∼30 ps. Images are arranged four to a strip with ∼60-ps temporal spacing between frames on a strip. By spacing the timing of the strips, a frame spacing of ∼15 ps is achieved. A framed resolution of ∼6-μm is achieved with this combination in a 400-μm region of laser-plasma x-ray emission in the 2- to 8-keV energy range. A principal use of the microscope is to measure the evolution of the implosion stagnation region of cryogenic DT target implosions on the University of Rochester's OMEGA Laser System [T. R. Boehly et al., Opt. Commun. 133, 495 (1997)]. The unprecedented time and spatial resolutions achieved with this framed, multi-image KB microscope have made it possible to accurately determine the cryogenic implosion core emission size and shape at the peak of stagnation. These core size measurements, taken in combination with those of ion temperature, neutron-production temporal width, and neutron yield allow for inference of core pressures, currently exceeding 50 Gbar in OMEGA cryogenic target implosions [Regan et al., Phys. Rev. Lett. 117, 025001 (2016)].

CBP derivatives dendronized self-host TADF dendrimer: Achieving efficient non-doped near-infrared organic light-emitting diodes

A self-host thermally activated delayed fluorescence (TADF) dendrimer, namely MPPA-MCBP, for solution-processed nondoped near-infrared organic light-emitting diodes (OLEDs) was designed and synthesized, in which the bipolar CBP derivatives is introduced to render balanced charge transportation. This structural modification that the dendrons are well-bounded by the flexible alkyl chains, which can efficiently reduce the intermolecular interactions between the emissive cores and ensure the stable operation of the solution-processed device. As a result of the spin-coated OLEDs employing MPPA-MCBP as the host-free near-infrared emitter exhibits a highest external quantum efficiency (EQE) of 0.62% and a peak wavelength at 698 nm, which indicates the design of self-host TADF dendrimers containing bipolar dendrons will be a promising strategy to improve the electroluminescent performance of solution-processed nondoped device.

Revisiting an Ongoing Debate: What Role Do Surface Groups Play in Silicon Nanocrystal Photoluminescence?

The origin of photoluminescence (PL) in silicon nanocrystals (SiNCs) remains a subject of considerable debate. Size-dependent PL that supports the quantum confinement model has been proposed by several researchers. On the other hand, SiNC PL arising from surface states that are independent of nanocrystal size has also been shown. This work addresses the origin of surface-functionalized SiNC PL as relating to surface states and the NC size. SiNCs of different sizes (3 and 5 nm diameters) were prepared with three distinct surface chemistries. Steady-state and time-resolved PL measurements were performed at temperatures ranging from 37 to 377 K. Temperature-dependent luminescence consistent with core emission was observed for alkyl-terminated SiNCs, while alkylamine-functionalized SiNCs displayed minimal temperature-dependent luminescence, consistent with a charge-transfer mechanism. Lightly oxidized alkyl SiNCs had similar emission profiles to alkyl SiNCs; however, they showed longer luminescence lifetimes ...

ALMA Images of the Orion Hot Core at 349 GHz

Abstract We present ALMA images of the dust and molecular line emission in the Orion Hot Core at 349 GHz. At 0.″2 angular resolution the images reveal multiple clumps in an arc ∼1″ east of Orion Source I, the protostar at the center of the Kleinmann–Low Nebula, and another chain of peaks from IRc7 toward the southwest. The molecular line images show narrow filamentary structures at velocities >10 km s−1 away from the heavily resolved ambient cloud velocity ∼5 km s−1. Many of these filaments trace the SiO outflow from Source I, and lie along the edges of the dust emission. Molecular line emission at excitation temperatures 300–2000 K, and velocities >10 km s−1 from the ambient cloud, suggest that the Hot Core may be heated in shocks by the outflow from Source I or from the Becklin–Neugebauer (BN)/SrcI explosion. The spectral line observations also reveal a remarkable molecular ring, ∼2″ south of SrcI, with a diameter ∼600 au. The ring is seen in high-excitation transitions of HC3N, HCN v2 = 1, and SO2. An impact of ejecta from the BN/SrcI explosion with a dense dust clump could result in the observed ring of shocked material.

Attosecond time delays in the valence photoionization of xenon and iodine at energies degenerate with core emissions

SynopsisWe perform time-dependent local density functional calculations of the quantum phase and Wigner-Smith time delays in the valence photoionization of Xe versus I atoms at higher energies where coupling with the core emission becomes important. Results for the 5s emission are presented.

The prevalence of core emission in faint radio galaxies in the SKA Simulated Skies

Empirical simulations based on extrapolations from well-established low-frequency ($< 5$ GHz) surveys fail to accurately model the faint, high frequency ($>10$~GHz) source population; they under-predict the number of observed sources by a factor of two below $S_{18~\rm GHz} = 10$ mJy and fail to reproduce the observed spectral index distribution. We suggest that this is because the faint radio galaxies are not modelled correctly in the simulations and show that by adding a flat-spectrum core component to the FRI sources in the SKA Simulated Skies, the observed 15-GHz source counts can be reproduced. We find that the observations are best matched by assuming that the fraction of the total 1.4-GHz flux density which originates from the core varies with 1.4-GHz luminosity; sources with 1.4-GHz luminosities $< 10^{25} \rm W \, Hz^{-1}$ require a core fraction $\sim 0.3$, while the more luminous sources require a much smaller core fraction of $5 \times 10^{-4}$. The low luminosity FRI sources with high core fractions which were not included in the original simulation may be equivalent to the compact `FR0' sources found in recent studies.

Full Protection of Intensely Luminescent Gold(I)-Silver(I) Cluster by Phosphine Ligands and Inorganic Anions.

An intensely luminescent gold(I)-silver(I) cluster [(C)(AuPPhpy2 )6 Ag6 (CF3 CO2 )3 ](BF4 )5 (PPhpy2 =bis(2-pyridyl)phenylphosphine) (3) is synthesized by the reaction of [(C)(AuPPhpy2 )6 Ag4 ](BF4 )6 with AgCF3 CO2 . All eight faces of the octahedral C@Au6 core in 3 are capped, that is, six faces are capped by silver ions and two by tetrafluoroborates. Cluster 3 is intensely luminescent in solution with a quantum yield of 92 %. Ligation of CF3 CO2- ions is vital for the construction and emission properties of 3, as confirmed by DFT calculations. BF4- ions are involved in the protecting sphere of the metal core, as evidenced by 19 F NMR data. The participation of phosphines, CF3 CO2- , and BF4- ions in the protection of the emissive core and the enhancement of the rigidity of the cluster result in the high emission efficiency. This is the first example of organic ligands and inorganic anions forming a rigid protecting sphere for luminescent coinage-metal clusters.

Full Protection of Intensely Luminescent Gold(I)–Silver(I) Cluster by Phosphine Ligands and Inorganic Anions

AbstractAn intensely luminescent gold(I)–silver(I) cluster [(C)(AuPPhpy2)6Ag6(CF3CO2)3](BF4)5 (PPhpy2=bis(2‐pyridyl)phenylphosphine) (3) is synthesized by the reaction of [(C)(AuPPhpy2)6Ag4](BF4)6 with AgCF3CO2. All eight faces of the octahedral C@Au6 core in 3 are capped, that is, six faces are capped by silver ions and two by tetrafluoroborates. Cluster 3 is intensely luminescent in solution with a quantum yield of 92 %. Ligation of CF3CO2− ions is vital for the construction and emission properties of 3, as confirmed by DFT calculations. BF4− ions are involved in the protecting sphere of the metal core, as evidenced by 19F NMR data. The participation of phosphines, CF3CO2−, and BF4− ions in the protection of the emissive core and the enhancement of the rigidity of the cluster result in the high emission efficiency. This is the first example of organic ligands and inorganic anions forming a rigid protecting sphere for luminescent coinage‐metal clusters.

A Decade of Hα Transits for HD 189733 b: Stellar Activity versus Absorption in the Extended Atmosphere

Abstract HD 189733 b is one of the most well studied exoplanets due to its large transit depth and host star brightness. The focus on this object has produced a number of high-cadence transit observations using high-resolution optical spectrographs. Here we present an analysis of seven full Hα transits of HD 189733 b using HARPS on the 3.6 meter La Silla telescope and HIRES on Keck I, taken over the course of nine years from 2006 to 2015. Hα transmission signals are analyzed as a function of the stellar activity level, as measured using the normalized core flux of the Ca ii H and K lines. We find strong variations in the strength of the Hα transmission spectrum from epoch to epoch. However, there is no clear trend between the Ca ii core emission and the strength of the in-transit Hα signal, although the transit showing the largest absorption value also occurs when the star is the most active. We present simulations of the in-transit contrast effect and find that the planet must consistently transit active latitudes with very strong facular and plage emission regions in order to reproduce the observed line strengths. We also investigate the measured velocity centroids with models of planetary rotation and show that the small line profile velocities could be due to large velocities in the upper atmosphere of the planet. Overall, we find it more likely that the measured Hα signals arise in the extended planetary atmosphere, although a better understanding of active region emission for active stars such as HD 189733 is needed.

Emission transformation in CdSe/ZnS quantum dots conjugated to biomolecules

The variation of photoluminescence (PL) spectra in CdSe/ZnS quantum dots (QDs) at the conjugation to antibodies (ABs) has been investigated and discussed in this paper. Two types of CdSe/ZnS QDs with different CdSe core sizes (5.4 and 6.4nm) and emissions (605 and 655nm) were studied before and after the conjugation to anti-Interleukin-10 (IL-10) and anti-Pseudo rabies virus (PRV) ABs. The PL high energy shift and asymmetric shape of PL bands have been detected in bioconjugated QDs. Note that the bioconjugation impact on spectral characteristics of CdSe/ZnS QD emission has been not studied yet in details. The surface enhanced Raman scattering (SERS) effect is revealed in bioconjugated CdSe/ZnS QDs. The SERS effect testifies that the excitation light used at the Raman study generates the electric dipoles in AB molecules. At the same time, the permanent position of LO-phonon Raman lines in Raman spectra of nonconjugated and bioconjugated QDs confirms that QD materials do not change at the bioconjugation. It is shown as well that the compressive strains do not play any role in the PL high energy shift in bioconjugated QDs. PL spectra of pure anti IL-10 ABs, anti PRV ABs, a phosphate buffer saline (PBS) and PL spectrum dependences versus excitation light intensities have been investigated as well. Finally, the PL spectrum transformation in bioconjugated QDs is attributed to varying the quantum confinement effect in CdSe/ZnS QDs and the energy band profiles in QD cores. Both these effects are stimulated by the electromagnetic field of excited AB dipoles. The obtained results can be useful for sensitivity improving the QD bio-sensors.

Periodic longitude-stationary non-drift emission in core-single radio pulsar B1946+35

Radio pulsar PSR B1946+35 is a classical example of a core/cone triple pulsar where the observer's line of sight cuts the emission beam centrally. In this paper, we perform a detailed single-pulse polarimetric analysis of B1946+35 using sensitive Arecibo archival and new observations at 1.4 and 4.6 GHz to re-establish the pulsar's classification wherein a pair of inner conal ‘outriders’ surround a central core component. The new 1.4 GHz observation consisted of a long single pulse sequence (PS) of 6678 pulses, and its fluctuation spectral analysis revealed that the pulsar shows a time-varying amplitude modulation, where for a thousand periods or so, the spectra have a broad low frequency ‘red’ excess and then at intervals they suddenly exhibit highly periodic longitude-stationary modulation of both the core and conal components for several hundred periods. The fluctuations of the leading conal and the core components are in phase, while those in the trailing conal component in counterphase. These fluctuation properties are consistent with shorter PS analyses reported in an earlier study by Weltevrede, Edwards & Stappers (2006) and Weltevrede et al. (2007) as well as in our shorter PS data sets. We argue that this dual modulation of core and conal emission cannot be understood by a model where subpulse modulation is associated with the plasma |${\boldsymbol E}$| × |${\boldsymbol B}$| drift phenomenon. Rather, the effect appears to represent a kind of periodic emission-pattern change over time-scales of ∼18 s (or 25 pulsar periods), which has not been reported previously for any other pulsar.

ALMA Observations of Vibrationally Excited HC3N Lines Toward Orion KL

Abstract We present high spatial resolution ALMA observations of vibrational transitions of HC3N toward Orion KL in the 214–247 GHz frequency band. 41 transitions of HC3N in 7 vibrationally excited states, and 23 transitions of 13C isotopologues of HC3N in 2 vibrational states are detected. The line images show that vibrationally excited HC3N lines originate mainly from the hot core of Orion and IRc7. The images of HC3N vibrationally excited lines show that the line emission peaks associated with the hot core move from south to northeast as increases. Based on multiple transitions of each vibrationally excited state, we performed local thermodynamic equilibrium calculations in the XCLASS suite toward the hot core and IRc7 positions. Generally, transitions in highly excited states have higher rotational temperatures and lower column densities. The rotational temperatures and column densities of the hot core range from 93 to 321 K, and from to cm−2, respectively. Lower rotational temperatures ranging from 88 to 186 K and column densities from to cm−2 are obtained toward IRc7. The facts that the hot core emission peaks of vibrationally excited HC3N lines move from south to northeast with increasing , and that higher-energy HC3N lines have higher rotational temperatures and lower column densities, appear to support that the hot core is externally heated. The emission peaks are moving along the major axis of the SiO outflow, which may indicate that higher-energy HC3N transitions are excited by interaction between pre-existing dense medium and shocks generated by SiO outflows.

Self-Host Blue Dendrimer Comprised of Thermally Activated Delayed Fluorescence Core and Bipolar Dendrons for Efficient Solution-Processable Nondoped Electroluminescence.

A self-host thermally activated delayed fluorescence (TADF) dendrimer POCz-DPS for solution-processed nondoped blue organic light-emitting diodes (OLEDs) was designed and synthesized, in which the bipolar phosphine oxide carbazole moiety was introduced by alkyl chain to ensure balanced charge transfer. The investigation of physical properties showed that the bipolar dendrons not only improve the morphological stability but also restrain the concentration quenching effect of the TADF emissive core. The spin-coated OLEDs featuring POCz-DPS as the host-free blue emitter achieved the highest external quantum efficiency (7.3%) and color purity compared with those of doped or nondoped devices based on the parent molecule DMOC-DPS, which indicates that incorporating the merits of encapsulation and bipolar dendron is an effective way to improve the electroluminescent performance of the TADF emitter used for a solution-processed nondoped device.

Two‐Color Emitting Colloidal Nanocrystals as Single‐Particle Ratiometric Probes of Intracellular pH

Intracellular pH is a key parameter in many biological mechanisms and cell metabolism and is used to detect and monitor cancer formation and brain or heart diseases. pH‐sensing is typically performed by fluorescence microscopy using pH‐responsive dyes. Accuracy is limited by the need for quantifying the absolute emission intensity in living biological samples. An alternative with a higher sensitivity and precision uses probes with a ratiometric response arising from the different pH‐sensitivity of two emission channels of a single emitter. Current ratiometric probes are complex constructs suffering from instability and cross‐readout due to their broad emission spectra. Here, we overcome such limitations using a single‐particle ratiometric pH probe based on dot‐in‐bulk CdSe/CdS nanocrystals (NCs). These nanostructures feature two fully‐separated narrow emissions with different pH sensitivity arising from radiative recombination of core‐ and shell‐localized excitons. The core emission is nearly independent of the pH, whereas the shell luminescence increases in the 3–11 pH range, resulting in a cross‐readout‐free ratiometric response as strong as 600%. In vitro microscopy demonstrates that the ratiometric response in biologic media resembles the precalibralation curve obtained through far‐field titration experiments. The NCs show good biocompatibility, enabling us to monitor in real‐time the pH in living cells.

THE MOUNT WILSON OBSERVATORY S-INDEX OF THE SUN

ABSTRACT The most commonly used index of stellar magnetic activity is the instrumental flux scale of singly ionized calcium H &amp; K line core emission, S, developed by the Mount Wilson Observatory (MWO) HK Project, or the derivative index . Accurately placing the Sun on the S scale is important for comparing solar activity to that of the Sun-like stars. We present previously unpublished measurements of the reflected sunlight from the Moon using the second-generation MWO HK photometer during solar cycle 23 and determine cycle minimum , amplitude , and mean . By establishing a proxy relationship with the closely related National Solar Observatory Sacramento Peak calcium K emission index, itself well correlated with the Kodaikanal Observatory plage index, we extend the MWO S time series to cover cycles 15–24 and find on average , , . Our measurements represent an improvement over previous estimates that relied on stellar measurements or solar proxies with non-overlapping time series. We find good agreement from these results with measurements by the Solar-Stellar Spectrograph at Lowell Observatory, an independently calibrated instrument, which gives us additional confidence that we have accurately placed the Sun on the S-index flux scale.

Markedly enhanced up-conversion luminescence by combining IR-808 dye sensitization and core-shell-shell structures.

Rare-earth-doped up-conversion nanoparticles (UCNPs), which are capable of converting infrared light to shorter-wavelength photons, have attracted worldwide attention due to their unique characteristics. However, the emission brightness of UCNPs is greatly limited by the unsatisfactory absorptivity of lanthanide ions. Herein, we adopted a novel strategy to enhance the up-conversion intensity using NIR dye IR-808 as an antenna to sensitize the core-shell-shell structured NaGdF4:Yb,Er@NaGdF4:Yb@NaNdF4:Yb UCNPs. When excited with 808 nm light, the IR-808 emitted a broadband peak, which perfectly overlapped with the absorption of Nd3+ and Yb3+ ions. Thus, the active shell of NaNdF4:Yb can efficiently capture the emitted NIR photons and transfer them to the transition layer of NaGdF4:Yb. The transition layer acted as an energy bridge to connect the active shell and up-converting zone, avoiding the energy back-transfer from the activators to Nd3+ ions. The optimized dye sensitization combined with the well-designed core-shell-shell structure tremendously enhances the NIR photon absorptivity of UCNPs and eliminates the deleterious cross-relaxation between the activators and sensitizers, eventually leading to dramatic enhancement of the up-conversion intensity. This study provides a new insight into the dye-sensitized up-conversion luminescence of rare earth-based nanoparticles and facilitates their practical applications.

Aspects of emission variation in CdSeTe/ZnS quantum dots conjugated to antibodies

CdSeTe/ZnS quantum dots (QDs) with the emission peak at 705 nm have been studied comparatively in the non-conjugated state and after bioconjugation to anti-pseudo rabies virus antibodies (ABs) by means of photoluminescence (PL) and Raman scattering methods. It is revealed that PL spectra of QDs vary significantly after conjugating to ABs. In PL spectra of non-conjugated QDs only one PL band of Gaussian shape peaked at 1.76–1.78 eV and related to exciton emission in the CdSeTe core has been detected. The PL spectra of bio-conjugated QDs demonstrate the high energy spectral shift and asymmetric shape of PL bands. The study of Raman scattering spectra permits to estimate the CdSeTe alloy composition and to detect the surface enhanced Raman scattering (SERS) effect for bioconjugated QDs. The last fact testifies on the interaction of excitation light electromagnetic field with the electric dipoles excited in ABs. The optical band gap in CdSeTe core has been calculated numerically versus core radius on the base of the effective mass approximation model. Then the energy band diagrams for non-conjugated and bio-conjugated states of CdSeTe/ZnS QDs have been designed. It is revealed the type II quantum well in CdSeTe core that explains the optical transition at 705 nm in the wide band gap CdSeTe alloy. The analysis has shown that AB dipoles excited in bio-conjugated QDs stimulate changing the profile of QD energy band diagram that manifests itself in the mentioned PL spectrum transformations. Actually, the study of PL spectrum varying in CdSeTe/ZnS QDs conjugated to specific antibodies can be an informative tool in biology and medicine for early medical diagnostics.

Constructing a Novel Dendron for a Self-Host Blue Emitter with Thermally Activated Delayed Fluorescence: Solution-Processed Nondoped Organic Light-Emitting Diodes with Bipolar Charge Transfer and Stable Color Purity.

Self-host thermally activated delayed fluorescence (TADF) materials have recently been identified as effective emitters for solution-processed nondoped organic light-emitting diodes (OLEDs). However, except for the carbazole unit, few novel dendrons have been developed to build self-host TADF emitters. This study reports two self-host blue materials, tbCz-SO and poCz-SO, with the same TADF emissive core and different dendrons. The influence of the peripheral dendrons on the photophysical properties and electroluminescent performances of the self-host materials were systematically investigated. The transient fluorescence and electroluminescence spectra indicated that the diphenylphosphoryl carbazole units could effectively encapsulate the emissive core to reduce the concentration quenching effect and to enhance reverse intersystem crossing. By using tbCz-SO and poCz-SO as host-free blue emitters, the performance of the solution-processed nondoped OLED device demonstrated that a more balanced charge transfer from the bipolar dendrons would offer a better current efficiency of 10.5 cd A-1 and stable color purity with Commission Internationale de L'Eclairage units of (0.18, 0.27).

Design strategy of yellow thermally activated delayed fluorescent dendrimers and their highly efficient non-doped solution-processed OLEDs with low driving voltage

We designed and synthesized two dendrimers TA-Cz and TA-3Cz with TADF characteristics by using non-conjugated aliphatic chains carbazole/tricarbazole as peripheral dendrons. Both dendrimers possess excellent thermal and morphological stabilities. Introduced the phenyl bridge to increase the distance of the emission core TA between donor (D) and acceptor (A) is a promising route to simultaneously achieve small singlet–triplet energy splitting (ΔEST) and enhanced PL quantum yields (PLQYs). Furthermore, non-conjugated aliphatic chains carbazole/tricarbazole dendrons were conveniently introduced to the TADF core, which can effective encapsulate the emission core to restrain the concentration quenching effect and make the fluorescence of the core independent. By utilizing TA-3Cz emitter as the non-doped solution-processed emissive layers, the resulting yellow OLED achieved low driving voltage of 2.4 V and superior external quantum efficiency of 11.8%. Thus, our results here provide a facile strategy to obtain highly efficient non-doped solution-processed OLEDs by employing the reasonable molecular design of the TADF core and the utilization of flexible alkyl chain.